Arylamides of 3-hydroxy-phenyl-aryl-amine-carboxylic acids and process of making same



Patented July 26, 1932 UNITED STATES PATENT OFFICE LEOIPOLD LASKA AND OSKAR HALLER, OF OFFENBACH-ON-THE-MAIN, GERMANY, AS-

SIGNORS TO GENERAL ANILINE WORKS, INC., OF NEW YORK, N. Y., A CORPORATION OF DELAWARE ARYLAMIDES 0F 3-HYDROXY-PHENYL-ARYL-AMINE-CARBOXYLIO ACIDS AND PROCESS OF MAKING SAME' No Drawing. Application filed February 20, 1930, Serial No. 430,130, and in Germany February 27, 1929.

The present invention relates to new arylamides of 3-hydroXy-phenylarylamine carboxylic acids which correspond probably to the general formula:

m wherein R means a radical of the benzene series, R any aromatic radical, X means hydrogen or anacyl-group and n the number l or 2, and to a process of making same.

The process being the object of the present 1" invention comprises condensing in the presence of an acid condensing agent an arylamino-phenol-carboxylic acid of the probable general formula:

wherein X and R have the above signification, which is obtainable by treating the corresponding arylamino-phenol with carbonic acid under pressure (see U. S. application Serial No. 407,274, filed November 14, 1929) and acylating advantageously the ,carboxylic acid M) thus produced, with an arylamine ofthe general formula:

(Han, R;

wherein n and R have the above signification whereto a diluent may be admixed.

As arylamino-phenol-carboXylic acids suitable for this process may be named, for instance, 3-phenylamino-phenol-carboxylic acid and its halogen-, alkyl-, alkoxyor aryloxy- 4:1 derivatives having these groups attached to the phenylamino radical, which compounds are described in U. S. application Serial No. 407 ,274, filed November 14, 1929. Appropriate arylamines are, for instance, aniline, its substitution products containing halogen-, alkyl-, alkoxyor nitro-groups or simultaneously several of these groups, furthermore amino phenols, amino cresols, amino-naphthols, amino-anthraquinones, diamino-naphthalenes, diamino-diaryls.

In the case of using diamino-compounds one or two molecular proportions of the carboXylic-acid may be subjected to the action of the diamine.

Those of the new arylamides are of a special value which correspond to the propable general formula:

Gem-@o ONH III ,7 \OH wherein the benzene nucleus signified by I contains halogen-, alkyl-, alkoxyor aryloxygroups or several of these groups and the nucleus signified by III may contain halogen, alkyl-, alkoxyor nitro-groups or several of these groups.

When the compounds obtained by this process contain an 'acyl-group (X of the above formulae being acyl) this acyl-group may be split off by an after-treatment with saponifying means.

The new compounds thus produced are distinguished by a great affinity to the vegetable fiber being manifold that of the corresponding aryl-amides of salicylic acid. For this reason they represent valuable intermediates for the production of dyestuffs.

In orderto further illustrate our invention the following examples are given, the parts being by weight and all temperatures in centigrade degrees, but it is however to be understood, that our invention is not limited to the particular products or reacting conditions mentioned therein I Ewample 1 22.9 parts of 3-hydroxy-diphenylaminecarboXylic acid, obtainable according to the example of U. S. application Serial No.

407274, of 19.29, are heated in 300 parts of toluene to 60. Thereto parts of aniline are added. At 6070 6 parts of phosphorous trichloride are allowed to run in and the whole is heated to boiling for about 3 hours until the evolution of hydrochloric acid has ceased. The condensation productis purified by dissolving it in a dilute caustic soda lye and by precipitating with carbonic acid. ll hen recrystallized from Xylene the new 3 hydroriy diphenyl amine carboxylic acid anilide of the probable formula:

I O U represents colorless glittering needles meltmg at 186 (uncorrected).

Earning/n 2 oo o 22.. parts of 3-hydroiiy-diphenylaniinecarboxylic acid are treated with l-l.3 parts of Q-amino-naphthalene in 300 parts of Xylene with the addition of (3 parts of phosphorus trichloride and the reaction product is purified in the manner described in E2:- ample 1. The B-naphthylamide of S-liydroXy-diphenylamine-carboxylic acid of the probable formula:

I O H crystallizes from chloro-benzene in colorless needles melting 208 (uncorrected).

Eaimnple 3 22.9 parts of 3-hydroxy-diphenylaminecarboXylic acid are likewise condensed with 12.2 parts of dianisidine in the presence of 300 parts of chloro-beincene and 0 parts of phosphorus trichloride. The new product isolated as above desribed represents when recrystallized from ortao-dichloro-benzene a reddish colored amorphous powder melting above 340 (uncorrected). It corresponds to the probable formula: 7

\ 1 l OH OCH OH OCHa Ewmn pZe 4, 22.9 parts of 3hydro. :y-diphenylaminecarboxylic acid, parts of to diaminonaphthalene, 0 parts of phosphorus t-richlonide and 300 parts of chloro-benzene are treated as described in the foregoing examples. The arylainide thus obtained corresponds probably to the formula:

It crystallizes from intro-benzene in nearly colorless small needles melting at 293 (uncorrected) Example parts of 8-hydro);y-t-chloro-diphenylamine-carboxylic acid and 11 parts of meta-aminophenol are dissolved at -70 in 300 parts of dimethylaniline. Then 6 parts of phosphorus trichloride are added at this temperature and the mass is maintained at 120 for 8-10 hours. The reaction product introduced while stirring into an excess of dilute hydrochloric acid. The residue is washed and freed from dimethylaniline, if any. by s eam distillation after being rendered alkaline with a soda solution. The remaining); 3-hydi-oxy-l-chloro-diphenylamine carboxylic acid meta-hydroxy-anilide of the probable formula OH OH crystallizes from glacial acetic acid as sandlike powder melting at 210212 (uncorrected).

Emomplc 6 cultly soluble, even in the hot, in most of the organic solvents. probable formula It corresponds to the Ema-mp Ye 21-.3 parts of 3hydroxy-2methyl-diphenylamine-carboxyhc acid, 11 parts of paraamino-phenol, 6 parts of phosphorus trichloride and 500 parts of toluene are condensed as described above. The formed para-hydroxy-anilide of 3-hydroxy-2-methyl-diphenylamine-carboxylic acid of the probable formula:

shows when crystallized from xylene the melting point 230231 (uncorrected).

E wample 8 7 8 parts of the sodium salt of 3-hydroxydiphenylamine-carboxylic acid and 46 parts of para-nitro-aniline are mixed with 750 parts of xylene and then gradually with 20 parts of phosphorus trichloride. The temperature is kept at for some hours. Then the mass is rendered alkaline with sodasolution, the xylene is blown off by means of steam and the reaction product is purified by dissolving it in caustic soda lye and precipitating with carbonic acid. The new paranitro-anilide of 3-hydroxy-dipheny1aminecarboxylic acid of the probable formula:

crystallizes from glacial acetic acid in yellowish green needles melting at 211-212".

E wample 9 76.3 parts of S-hydroxy-diphenylaminecarboxylic' acid and parts of thionylchloride are introduced into 1000 parts of ligroine and the mixture is heated to boiling until it is dissolved. Then the ligroine and the excess of thionyl-chloride are distilled off in vacuo. The residue is mixed with 750 parts of toluene and 35.7 parts of orthotoluidine and the mixture is boiled until the evolution of hydrochloric acid has ceased. The mass is mixed with soda-solution until being alkaline and freed from toluene by steam. The reaction product is purified as described above. It represents the orthotoluidide of 3-hydroxy-di1: henylamine-carboxylic acid of the probable formula:

305.5 parts of N-acetyl-3-hydroxy-4- chloro-diphenylamine-carboxylic acid, prepared by longer boiling 3-hy-droxy-4'-chlorodiphenylamine-carboxylic acid with an excess of acetic acid anhydride, and 138 parts of meta-nitro-aniline are introduced into 3000 parts of ortho-dichloro-benzene. At 60-70 60 parts of phosphorus trichloride are gradually dropped in. The mass is maintained at 110 for some hours, then mixed with an excess of double-norl'nal caustic potash-lye. Orthod1chloro-benzene is removed by introducing steam and the remaining filtered solu- 4 tion is saturat d with carbonic acid. Thereby metanitro-anilide of 8-hydroxyy-chloros, diphenyl-amine-carboxylic acid precipitates. It corresponds to the probable formula:

\ OH N01 It crystallizes from ortho-dichloro-benzene and melts at 203.

E wample Z1 scribed above. It corresponds to the probable formula and melts when recrystallized from o-dichlorobenzene at 229.

E wample 12 A mixture of parts of 3-hydroxychloro-d1phenylam1ne-carboxylic acid, 172.5 arts of 6-chloro--n1tro-an1l1ne and 1500 parts of xylene is treated with 60 parts of phosphorus trichloride and the reaction mass is worked up as described in the foregoing examples.

The ortho-chloro-para-nitro-anilide of 3- hydroxy:-chloro diphenylamine-carboxylic 11:.

acid thus formed corresponds to the probable formula: 0

It melts when recrystallized from glacial acetic acid or from pyridine at 240.

The following table shows the properties of some further arylalnidcs prepared by the Melting P t Process Arylamide prepared from: Recrystalhzcd from: point:

a, n +aniline Chlorob nz i 202 Arylamide Prepared from: RCCIYSlfllllZOfl from: +0m1ismine g ggg +p-an iriine Chlorohcnzene 215217 +11: lroani linle Diclilorobenzene 213-214 Oxvd- 1 CL 1 & 0 3-iydroxy-B-c 1lor0-4-methyl +0-anisidinc Benzene 123-125 l I a y y r y p y +an lmc 0| v C h lorohemene 14G: amimmarboxylic acid +l-(:ll0l0 am no-toluene xylene 180 +anmnc Xvkm 740 +5-ci lorou ammotoluene R ylene 190 +p nitmflnmnc cmorobemcne D -lp-n i roani hne V Cnlorobenzenc 25g: +Bmanht1wmmine cmombummc jlflai apluliplainme I Cnlorooenzenc 2 1.) 3-hydr0xy-3-1nethy1diphenylll ,f i llf 2 1' +amine-carboXylic acid 1 b If aniline C ilero enzcne 1% J y +p-nitroaniline (hlcrobenzene 218 v g l i 4 +fi-naphthylamine (llllOYObCllZCllQ 3 fi 1 1 Om vnl'onc 3 hydrOW 4/ methvldiphenvl q fil-nziplniiylainine Llilorobenzcne 188 nnline mrboxvhc acid I1ny lrox \2.4 l 1tlll( )10 (l1pll0- +anilinc (llllOiOllLllZOIlO mxyhc {101d v +m-amin0phenol Xylene si 1 x +paniinoplicnol Xylene n-muoanihno 2 1c IlOYO JGDLCUC 242-2 13 +D-I1iiroaniline Clilorobcnzcne Dmhlommmene 3-hydroxy2-clilorodiphenylx*l',(d gg lg g m (m USA1770 D clilorobenzene 188: 0 +m aminophonol o Dienlorobenzcne 208-209 caustic so(la10luli0n +p-aniinophenol Do. lair-162 +0 anisi linc Xylene lea-107 v Y O +p-niiroaniline ClllOl'OllOIlZLllO 15 cllurolemene 2S0 3-hydroxy-3clilerodiphenyl amine-carhoxylie acid +aniline (hlnrohenzene 160 lfy'g 013 +o-anisidine Do. 137 p g +p-niirloakxliilline Chlorohcnzene o 1,. 1 1 ocess which comprises condensing 1n i '1 ,170 is 20%. w i: gtgg1 gg. g,g{3g2g m 1 th presence oi an acid condensing agent an amine-carboxylic acid +aniline +0-toluirline +p-t0luidine +o-chloroanilinc +p-eliloroani1ino +2.5- iichloroaniline +4-eliloro-2-aminotoluene +5-chlero2-aminotoluenc +p-aminoplienol +o-anisidiuc +5-chloro-Z-ainino anisolc +p-anisiiline +p-phenetidine +2-chlor0--i-nitroaniline +5-nitro-2aminotoluene +4-nitro-2-an1ino41nis0le +B-naphthylamine +1-aminoantl1raquinone +2-aminoanthraquinone +1.5diaminoanthraquinone (half its molecular proportion) +3-amino-carbazole 3 -hydroxy 2 IllQLl107i}'(ll17llC nylainine-carhoxylic acid +aniline +m-aminophenol i-p-aniinopheuol +pnitroaniline 3-hydroxy-4-met ho xyd ioli e nylaminccarboxylic acid +aniline 3-hydr0xy4 ph enoxyd iplienylaminc-cai'hoxylic acid +p-nitrcaniline 3-hy(lroxy-- i4 alimethyldh phenylamine-carhexylic acid +p-nitroauilinc +p-nitroaniliize +B-naphtirvla1nine 3-hydroxy "-meiliyl-4ehlorodinhenylamine-carboxylic acid +ziniline +p nitroaniline 3-hydroxy-2-methyl-5 ch1orodiphenylamincwarboxylic acid +p-nitroaniline 3-hydr0xy-3-1ncthyll-chlero- (liphenylaniine-carboxylie acid Glacial acetic acid Glacial acetic acid :lllL-lllllfllJlllZOl'lO (lilorobemene ihlorohenzcne Chlorohenzene Precipitated from its caustic SO(l1\1-0lL1llOH Dichlorobenzene Dichlorobenzene Dichlorohenzenc (hierom ne i' lilorohemelie (lilorelvcnrconc hloroheai'cene Chlorohenzene (hlorohcmzenc Chlorohenzcne Chloroh "e Chloroh Chleroh Chlmohemene Clilomlmnzeiie Xylene Xylene Chlorohcnzene smear 197 153 155*lilll mtorciow above 330 lainino-phenol-carboxylic acid. of the r probable general formula:

wherein X means hydrogen 0 an acyl-group and H stands for a radical of the benzene series which is obtainable by treating the corresponding arylamino-phenol with carbonic acid and acylating advantageously the carboxylie acid thus produced, with an arylamine of the general formula:

(ILN) n2 benzene (liphenyl, naphthalene 0r anthra qi none and 7L the number 1 or 2.

n. A rocess which comprises condensing in the presence of an acid condensing agent an arylamino-phenol-carboxyhc acid of the erobabie general formula coon (Hamel wherein R means any aromatic radical of the benzene, diphenyl, naphthalene or antln'aqumone series and a the number 1 or 2.

3. Process which comprises condensing in the presence of an acid condensing agent a 4-. chloro phenylamino-phenol carboxylic acid of the probable general formula:

wherein X means hydrogen or an acylgroup, which is obtainable by treating the corresponding arylamino-phenol with carbonic acid and acylating advantageously the carboxylic acid thus produced, with an arylamine of the general formula:

wherein R means any aromatic radical of the benzene, diphenyl, naphthalene or anthraquinone series and n the number 1 or 2.

4. As new compounds the arylamides of arylaminophenol-carboXylic acids corresponding to the probable general formula:

[ a-O m wherein R means a radical of the benzene series, R any aromatic radical of the benzene, diphenyl, naphthalene or anthraquinone series, X means hydrogen or an acyl-group and n the number 1 or 2 which are obtainable by treating the corresponding arylamino-phenols with carbonic acid, acylating advantageously the carboxylic acids thus produced and condensing with a corresponding arylamine, which compounds are amorphous or crystallized substances, having a definite melting point, difiiculty soluble in organic solvents, easily soluble in alkalies, distinguished by a great aflinity to the vegetable fiber.

5. As new compounds the arylamides of arylamino-phenol-carboxylic acids corresponding to the probable general formula:

l z lr wherein X means hydrogen or an acyl-group, Y means alkyl, alkoxy, aryloXy or halogen, R any aromatic radical of the benzene, diphenyl, naphthalene or anthraquinone series and n the number 1 or 2, which are obtainable by treating the corresponding aryla-minophenols with carbonic acid, acylating advantageously the carboxylic acids thus produced and condensing with a corresponding arylamine, which compounds are amorphous or crystallized substances, having a definite melting point, difficulty soluble in organic solvents, easily soluble in alkalies, distinguished by a great affinity to the vegetable fiber.

6. As new compounds the arylamides of arylamino-phenol-carboxylic acids corresponding tothe probable general formula:

on v wherein X means hydrogen or an acyl-group, R any aromatic radical of the benzene, diphenyl naphthalene or anthraquinone series and n the number 1 or 2, which are obtainable by treating the corresponding 3-(V-chlorophenylamino) -phenol with carbonic acid, acylating advantageously the carboxylic acids thus produced and condensing with a corresponding arylamine, which compounds are amorphous or crystallized substances, having a definite melting point, difiicultly soluble in organic solvents, easily soluble in alkalies, distinguished by a great afiinity to the'vegetable fiber.

7. As new compounds the arylamides of chloro-phenyl-amino-phenol-carboxylic acids corresponding to the probable general formula:

wherein Z means hydrogen, alkyl, alkoxy or chlorine, which are obtainable by treating the corresponding 3- (4-chloro-phenylamino) phenol with carbonic acid and condensing with an arylamine of the probable general formula HzN-ONO:

wherein Z has the above signification, which compounds are amorphous or crystallized substances, having a definite melting point, difiicultly soluble in organic solvents, easily soluble in alkalies, distinguished by a great aflinity to the vegetable fiber.

9. As a new compound the para-nitroanilide of 4-chloro-8-hydroxy-diphenylamine-earboxylic acid of the probable formula:

obtainable by treating the corresponding 3- (4-cl1loro-phenyl-a1nino)-phenol With carbonic acid and condensing with tflfitl'O-illliline, which compound is a crystallized substance, having its melting point at 229, dilficultly soluble in organic solvents, easily soluble in alkalies, distinguished by a great aflinity to the vegetable fiber.

10. As a new compound, the para-chloroanilide of 4E-chloro-3-hydroxy-diphenylaniine-carboxylic acid of the probable formula:

melting when recrystallized from chlorobenzene at 1S8-190, diflicultly soluble in organic solvents, easily soluble in alkalies, distinguished by a great affinity to the vegetable fiber.

11. As a new compound, the ortho-anisidide of atchloro-3-hydroxy-dipl1enyla1ninecarboxylic acid of the probable formula:

OCH:

melting when recrystallized from chlorobenzene at 142, diflicultly soluble in organic solvents, easily soluble in alkalies, distinguished by a great aflinity to the Vegetable fiber.

In testimony whereof, We aflix our signatures.

LEOPOLD LASKA. OSKAR I-IALLER. 

